颗粒物对混凝过程及超滤膜污染的影响

以nm-SiO₂和μm-SiO₂体系为研究对象,使用3种不同Al形态的混凝剂（AlCl₃、Al₁₃和Al₃₀）进行混凝-超滤实验,考察不同pH值下SiO₂去除率、出水余Al及混凝预处理对膜通量的影响,借助马尔文激光粒度仪、SEM、BET和AFM表征絮体性质及在超滤膜表面的分布和作用力.结果表明,nm-SiO₂体系中SiO₂去除率均低于μm-SiO₂体系,在纳米颗粒物体系中投加混凝剂后膜通量从0.68分别提升至0.96（AlCl₃）、0.86（Al₁₃）和0.87（Al₃₀）,微米颗粒物体系中投加3种混凝剂后膜通量从0.79提升至0.80~0.84.微米级颗粒物是颗粒间的碰撞,纳米级颗粒物主要以团聚态的形式碰撞.低聚态铝（Al_a）和颗粒物形成絮体的粒径均大于150μm,体系zeta电位为负与膜表面产生斥力;在中性条件下Al₁₃与颗粒物形成絮体的强度因子远高于AlCl₃和Al₃₀,中聚态铝（Al_b）将膜孔内部较小颗粒物堵塞形成的不可逆膜污染转移成膜孔表面的可逆膜污染;高聚态铝（Al_c）具有较强吸附架桥和网捕卷扫能力,无定形、不规则的团聚态小颗粒在这一过程中形成较大絮体缓解膜污染.     

混凝过程中铝盐水解聚合反应平衡的流体动力学控制

为了明确混凝过程中搅拌剪切等动力学因素对铝盐水解聚合反应平衡的影响,采用配制模拟水样作为混凝水系,用Ferron逐时络合比色法对水解产物形态进行表征,并将获取结果与用去离子水组成的纯净水系获取的结果进行对比分析.同时,研究了模拟混凝水系中搅拌剪切条件对铝盐水解反应产物形态分布的影响,考查了铝盐的碱化度和模拟混凝水系的pH值对混凝体系中搅拌剪切条件作用于铝盐水解产物形态分布的影响,并提出了体系搅拌剪切条件影响混凝水系中铝盐水解反应平衡的作用机理.结果表明,混凝过程中的铝盐水解产物形态分布明显受到体系搅拌剪切条件的影响,并且随着混凝水系中铝盐水解程度的增大和转化率的提高,铝盐的水解产物形态分布受到反应体系中搅拌剪切条件的影响加大.     

活性硅酸混凝剂在有机废水处理中的应用研究

以水玻璃,硫酸铝为主要原料制备一定比例铝离子的活性硅酸混凝剂(简称PSAA,以下同),试验其在处理一些典型的有机废水中的混凝特性及影响因素。实验结果表明,铝离子的添加量及溶液最终pH值对PSAA的混凝特性影响都很大.当SiO₂/Al3+(摩尔比)为1左右时,混凝效果最好;在pH4～10范围内,PSAA有着良好的混凝性能。      

聚合氯化铝镁钛的制备及结构表征

为提高铝基复合混凝剂的混凝效果,以AlCl₃、MgCl₂、TiCl₄为原料,通过共聚反应制备出无机复合高分子混凝剂PCAMT（聚合氯化铝镁钛）,并探究其混凝机理.采用Ferron（高铁试剂）逐时络合比色法、红外光谱、X-射线衍射谱图、扫描电镜与能谱分析（SEM-EDS）、Zeta电位对产物的Al形态、结构形貌、组成及混凝机理进行分析.结果表明:①采用单因素试验法获得最佳合成条件,即反应温度为60 ℃,Mg/Al（摩尔比,下同）为0.5,Ti/Al（摩尔比,下同）为0.5,OH/（Al+Mg+Ti）（摩尔比,下同）为0.6.②形态分析表明,反应温度、Mg/Al、Ti/Al,OH/（Al+Mg+Ti）对Al的形态分布均存在影响.随着反应温度的升高,n（Ala）（Ala在Al的水解聚合形态中所占摩尔分数,下同）先减后增,n（Alb）（Alb在Al的水解聚合形态中所占摩尔分数,下同）先增后减,n（Alc）（Alc在Al的水解聚合形态中所占摩尔分数,下同）逐渐减小;随着Mg/Al的增大,n（Ala）先减后增,n（Alb）、n（Alc）为先增后减的趋势;随着Ti/Al的增大,n（Ala）逐渐增加,n（Alb）逐渐减少,n（Alc）先增后减;随着OH/（Al+Mg+Ti）的增大,n（Ala）逐渐减少,n（Alb）、n（Alc）逐渐增加.③通过红外光谱、X-射线衍射,确定了PCAMT的结构组成,表明PCAMT是一种—OH桥联的铝镁钛复杂无定型聚合物,含有Al—OH—Mg与Ti—O—Ti新基团以及形成了Mg_1.5Ti_1.25O₄、Mg_1.2Ti_1.8O₅、Al₃Ti₅O₂等共聚物.④扫描电镜与能谱结果表明,PCAMT呈紧凑的空间立体网状形貌结构,利于发挥吸附架桥、网捕卷扫作用.⑤由PCAMT投加量对Zeta电位的影响分析可知,低投药量的混凝过程中起主导作用的是电中和作用,高投药量PCAMT处理原水的混凝机制以吸附架桥和网捕卷扫作用为主.研究显示,AlCl₃、MgCl₂和TiCl₄通过共聚反应,可生成具有更高聚合度的无定型共聚物PCAMT,利于电中和、吸附架桥和网捕卷扫,具有较好的混凝效果.      

信号分子强化改性挂膜沸石持续抑制沉积物中氨氮释放

为寻找一种长期有效的底泥修复方式,对沸石进行了改性并挂膜的实验.考察了4种铝盐[AlCl₃、 Al（NO₃）₃、 Al₂（SO₄）₃和KAl（SO₄）₂]改性挂膜沸石对上覆水中氨氮的去除情况.结果表明,AlCl₃改性挂膜沸石效果最佳,且最佳改性浓度为0.8 mol·L^-1.进一步分析添加信号分子OHHL后,AlCl₃改性挂膜、 NaCl改性挂膜和天然挂膜沸石抑制河流底泥中氮释放的持续性.其中AlCl₃改性挂膜沸石上附着的细菌量多,反硝化菌数量占比高（初始82.1%; 30 d后61.1%）,因此,生物再生率高（64.9%）,从而使得该沸石使用寿命长达8.5个月.可见,AlCl₃改性挂膜沸石能对底泥释放的氮负荷达到有效持续地抑制.     

玉米秸秆生物炭改善污泥脱水性能

本实验以玉米秸秆为原料,制备了生物炭和AlCl₃改性生物炭,研究了2种生物炭分别调理污泥后的脱水效果,并探讨了污泥脱水性能的改善机理.结果表明,经过2种生物炭调理后,污泥比阻（SRF）、泥饼含水率（MC）、污泥沉降体积指数（SV₃₀）、毛细抽吸时间（CST）均下降,污泥净产率（Y_N）升高,说明污泥脱水性能得到了改善,且AlCl₃改性生物炭对污泥脱水性能的改善效果明显优于生物炭.当AlCl₃（溶液浓度3mol/L）改性生物炭的用量为3g/L时,调理后的污泥SRF,MC,SV₃₀,CST分别降低至1.3×10¹²m/kg,81.9%,78.6%,35s,Y_N增加至17.8kg/（m²·h）.分析原因：一方面,经过生物炭调理后,泥饼中会形成一定的骨架结构,使得污泥中的水和EPS能够更容易地释放;另一方面,经过AlCl₃改性后,改性生物炭携带的正电荷（Al³⁺）能够与污泥颗粒所带的负电荷发生电中和作用,使得污泥颗粒更容易聚集,从而提高污泥的脱水效果.     

Nano-TiO2回收过程中SO42-对不同混凝剂混凝过程的影响

为了降低纳米TiO₂使用成本,采用不同混凝剂对纳米TiO₂悬浊液进行固液分离.通过考察浊度去除率、出水pH值的变化情况,并结合X射线光电子能谱（XPS）、傅里叶红外光谱（FTIR）、固体核磁（NMR）、扫描电镜（SEM）及能谱分析（EDS）表征,探究了纳米TiO₂回收过程中SO₄^2-对不同混凝剂混凝过程的影响.结果表明,当使用AlCl₃作混凝剂时（0.1mmol/L）,SO₄^2-浓度从0.0mmol/L增加到20.0mmol/L,浊度去除率降低了0.80%,絮体粒径从450μm下降到215 μm,而强度因子无明显变化.低聚合态的Al_a不与SO₄^2-结合,混凝过程中通过吸附架桥和网捕卷扫的作用形成大量无定形的Al （OH）₃.当使用Al₁₃作混凝剂时,再生长后絮体的粒径随着SO₄^2-浓度的增加而下降,S-O峰的红移证明有新的含S聚合物产生,Al 2p的峰均向较高的结合能移动证明生成的絮体不是Al （OH）₃.     

聚硅酸金属盐类混凝剂的絮凝机理研究

以粉煤灰、硫铁矿渣为原料制备出系列聚硅酸金属盐类絮凝剂。采用Ferron分光光度法对其形态分布规律进行了研究,结果表明:与其他无机高分子絮凝剂相比,聚硅酸金属盐类的最优形态Al_b 和Fe_b 含量明显增加,产品稳定性增强。从理论上初步分析了这类絮凝剂高效混凝的原因。      

初始pH值对连续投加铝盐混凝去除小分子有机物的影响机制

以污水厂二级出水中小分子有机物强化混凝去除为目的,提出了连续投加混凝工艺(CDC),并以水杨酸为模型小分子有机物,研究了初始pH值对CDC工艺去除效果的影响以及铝离子与水杨酸的络合特性.结果表明,初始pH值6时CDC工艺的去除率最高,比常规混凝工艺提升了13.8%.但是初始pH值5和7时CDC工艺的提升效果较小.三维荧光结果表明,不同pH值下水杨酸和铝离子的络合特性不同.X射线光电子能谱和电喷雾质谱结果表明,pH值5时CDC工艺前期主要生成1:1络合物Al(OH)(C₇H₄O₃)(H₂O)₂.其络合作用强烈,稳定性较高,难以从水中去除.pH值6时前期主要生成中等聚合铝(如原位Al₁₃),其与水杨酸形成的络合物可以参与到铝离子的生长过程,最终生成表面崎岖形态松散的珊瑚礁状絮体,强化了水杨酸的去除.pH值7时,主要生成不定形氢氧化铝,通过絮体表面吸附小分子有机物.     

阴极电解液对Cd污染红壤电动修复的影响

针对土壤重金属电动修复过程中阴极电解室pH升高会对重金属的去除产生不利影响的问题,利用Fe3+/Fe2+、Cu2+/Cu标准电极电位较高的优势,以人工模拟Cd污染红壤为研究对象,对不同阴极电解液[Fe（NO₃）₃、CuSO₄、柠檬酸]的电动修复效果进行系统分析.结果表明:分别将Fe（NO₃）₃、CuSO₄、柠檬酸加入阴极电解室中,pH均控制在2~3,电动修复10 d后发现,将Fe（NO₃）₃溶液、CuSO₄溶液和柠檬酸作为阴极电解液均可以有效控制阴极室的pH,CuSO₄溶液、柠檬酸的加入对土壤中Cd的去除效果较差,而且Cu2+的加入增加了土壤重金属二次污染的风险.相对于CuSO₄、柠檬酸试验组,Fe（NO₃）₃试验组土壤中Cd的去除率较高（大于87.27%）,Fe（NO₃）₃试验组对土壤中Cd的修复效果也最为明显,土壤中w（Cd）由阴极附近的75.95 mg/kg降至阳极附近的9.13 mg/kg.分析电动修复后各试验组中不同形态Cd在Cd总量中所占比例的分析,结果显示,w（弱酸提取态Cd）所占比例由初始的74.57%最高可达到92.69%[Fe（NO₃）₃试验组],表明Fe（NO₃）₃的加入有助于促进土壤中Cd的迁移.研究显示,相比于CuSO₄溶液、柠檬酸,Fe（NO₃）₃溶液作为阴极电解液在控制阴极电解室pH升高的前提下,显著促进了土壤中Cd的解吸和迁移,并达到最佳修复效果.      

铝盐混凝剂的混凝效果与残留铝含量和组分之间的关系研究

研究了氯化铝、硫酸铝、聚合氯化铝(poly-aluminum chloride, PAC)3种铝盐混凝剂在腐殖酸-高岭土模拟水样中的应用,以比较3种混凝剂在该水样中的混凝效果与残留铝含量和组分之间的关系.结果表明, 3种铝盐混凝剂在试验选取的投加量下对浊度和UV254的去除率最高可达90%左右,PAC能在较高的投加量下达到较好的混凝效果;较高投加量下PAC混凝沉淀出水中残留总铝含量为0.9 mg/L左右,余铝率为-3.0%左右,均明显低于传统的铝盐混凝剂;3种混凝剂混凝处理腐殖酸-高岭土模拟水样时,残留铝均大部分以溶解性总铝的形式存在,且溶解性有机铝在总溶解性铝中所占比例较大;PAC在腐殖酸-高岭土混凝沉淀出水中残留总铝的含量下降最快,且能够有效降低出水中毒性较大的溶解性铝的含量,其混凝沉淀出水中残留总溶解性铝含量为0.6 mg/L左右.     

Al13形态在混凝中的作用机制

从铝的水解形态转化角度考察了铝盐在高碱度和高有机物浓度水体中的混凝行为.结果表明,铝盐的混凝效能是与混凝过程中的Al₁₃含量成正比.高投药量时氯化铝(AlCl₃)既可以有效调节水体pH值又能在混凝过程中原位水解产生较多的Al₁₃形态,因而混凝效能要高于聚合氯化铝(PACl).在铝盐混凝中,调节pH值到6～7之间可以控制铝形态分布从而达到提高混凝效能和减少残留铝的目的.在调节pH值强化混凝的方法中使用传统铝盐的效果要好于无机高分子絮凝剂.     

Preparation of high concentration polyaluminum chloride with high content of Alb or Alc

A novel membrane distillation concentration method was used to prepare high concentration polyaluminum chloride (PACl) with high content of Al_b or Al_c. 2.52 mol/L PACl₁ with 88% Al_b and 2.38 mol/L PACl₂ with 61% Al_c were successfully prepared. Three coagulants, AlCl₃, PACl₁ and PACl₂ were investigated on their hydrolysis behavior and speciation under different conditions. The effects of pH and dilution ratio on Al species distribution were investigated by ferron assay. Experimental result showed that pH had a significant effect on Al species distribution for the three coagulants. Dilution ratio had little effects on Al_b and Al_c distribution in whole dilution process except the beginning for PACl₁ and PACl₂. The results indicated that transformation of Al depends largely on their original composition. AlCl₃ was the most unstable coagulant among these three coagulants during hydrolysis process. PACl₁ and PACl₂ with significant amounts of highly charged and stable polynuclear aluminum hydrolysis products were less affected by the hydrolysis conditions and could maintain high speciation stability under various conditions.     

不同铝聚合形态对聚合铝混凝效果的影响

通过氯化铝(铝单体或初聚物形态Ala)、高Alb含量聚合铝(中等聚合形态Alb)、高Alc含量聚合铝(铝溶胶等高聚合形态Alc)和工业PACl(不同聚合度铝的混合形态Alabc)对某水厂沉后水实际水样进行烧杯混凝实验,依据絮体生长状况、浊度、UV254、颗粒数和过滤指数等参数综合评价不同铝形态的混凝作用效果,从而得出铝的最佳混凝形态.结果表明,高Alb含量聚合铝对浊度去除较好;而高Alc含量聚合铝对于颗粒物和UV254的去除效果较佳.     

不同铝形态去除水中腐殖酸的混凝特性

制备了碱化度为2.4、以Al13,为主要成分的聚合铝PAC-All13和碱化度为2.4、以Al30为主要成分的高聚聚合铝PAC-Al30.采用烧杯混凝实验,通过絮体颗粒生长、电中和能力、pH和混凝剂投量对混凝效果的影响,比较了PAC-Al30、PAC-Al13,和AIC3,混凝去除水中腐殖酸的行为,并考察了水中残留铝的含量.实验结果表明,3种混凝剂的絮体形成能力由强到弱为PAC-Al30>PAC-Al13>AlCl3.与AlCl3相比, PAC-Al13和PAC-Al30的适用pH范围更宽,为5.0～8.0.PAC-Al30和PAC-Al13,的电中和能力差别不明显;由于更强的吸附和架桥作用,在低投量下PAC-Al30表现出更好的混凝效果,而且PAC-Al30比AlCl3和PAC-Al13有更宽的有效投量范围,为0.08～0.64mmol/L.对于腐殖酸含量为10m/L的水样,在pH为7.0,投量为0.16mmol/L下, PAC-Al30对腐殖酸去除率达到98.5%,此时出水残留铝浓度为0.066mg/L.结果证实Al30是可用于水中腐殖酸去除的一种新型的混凝/絮凝活性成.     

Effect of AlCl3 concentration on nanoparticle removal by coagulation

In recent years, engineered nanoparticles, as a new group of contaminants emerging in natural water, have been given more attention. In order to understand the behavior of nanoparticles in the conventional water treatment process, three kinds of nanoparticle suspensions, namely multi-walled carbon nanotube-humic acid (MWCNT-HA), multi-walled carbon nanotube-N,N-dimethylformamide (MWCNT-DMF) and nanoTiO₂-humic acid (TiO₂-HA) were employed to investigate their coagulation removal efficiencies with varying aluminum chloride (AlCl₃) concentrations. Results showed that nanoparticle removal rate curves had a reverse “U” shape with increasing concentration of aluminum ion (Al^3 +). More than 90% of nanoparticles could be effectively removed by an appropriate Al^3 + concentration. At higher Al^3 + concentration, nanoparticles would be restabilized. The hydrodynamic particle size of nanoparticles was found to be the crucial factor influencing the effective concentration range (ECR) of Al^3 + for nanoparticle removal. The ECR of Al^3 + followed the order MWCNT-DMF > MWCNT-HA > TiO₂-HA, which is the reverse of the nanoparticle size trend. At a given concentration, smaller nanoparticles carry more surface charges, and thus consume more coagulants for neutralization. Therefore, over-saturation occurred at relatively higher Al^3 + concentration and a wider ECR was obtained. The ECR became broader with increasing pH because of the smaller hydrodynamic particle size of nanoparticles at higher pH values. A high ionic strength of NaCl can also widen the ECR due to its strong potential to compress the electric double layer. It was concluded that it is important to adjust the dose of Al^3 + in the ECR for nanoparticle removal in water treatment.     

聚合氯化铝中纳米Al13电荷特性及其混凝效果

采用聚丙烯酰胺凝胶柱层析法分离纯化聚合氯化铝(PAC)中的Al₁₃形态,并采用Al-Ferron逐时络合比色法和ZATESIZER 3000HSA测定仪对分离所得纳米Al₁₃形态以及AlCl₃和PAC进行了分析表征和电荷特性的对比性研究;采用烧杯实验法对3个样品处理实际和模拟水样的混凝效果进行了对比性研究.Al-Ferron逐时络合比色法的结果表明,采用层析法分离可得到含量99%左右的纳米Al₁₃形态;电荷特性和混凝效果研究结果表明纳米Al₁₃形态较其它两者具有更好的除浊、除腐殖酸和脱色效果并且具有更强的电中和能力,因此Al₁₃形态是一种具有较高正电荷和较高的水解稳定性,在给水和废水处理中的一种较为有效的Al形态.     

Purification and characterization of Al13 species in coagulant polyaluminum chloride

Nano-Al₁₃ was separated and purified by four methods to investigate its characteristic, and was analyzed by Al-Ferron timed complexation spectrophotometer,²⁷ Al-NMR (nuclear magnetic resonance), and transmission electron microscopy (TEM). Coagulation efficiency of nano-Al₁₃, polyaluminum chloride (PAC), and AlCl₃ in synthetic water were also investigated by jar test. The dynamic process and aggregation state of kaolin suspensions coagulating with nano-Al₁₃, PAC, and AlCl₃ were also investigated. The experimental results indicated that the efficiency of gel column chromatography method was the highest for separating PAC solution with low Al concentration. Ethanol and acetone method was simple and could separated PAC solution with different Al concentrations, while silicon alkylation white block column chromatography method could separate PAC solution only with low Al concentration. The SO₄²−/Ba²⁺ displacement method could separate PAC solution with high Al concentration, but extra inorganic cation and anion could be introduced into the solution during the separation. The coagulation efficiency and dynamic experimental results showed that nano- Al₁₃ with a high positive-charged species was the main species of electric neutralization in coagulation process, and it could reduce the turbidity and increase the effective particles collision rate efficiently in coagulation process. Its coagulation speed and the particle size of coagulant formed were of greatest value in this study.     

Synchronous removal of CuO nanoparticles and Cu2+ by polyaluminum chloride-Enteromorpha polysaccharides: Effect of Al species and pH

Copper oxide nanomaterials have been extensively applied and can have serious impacts when discharged into the aquatic environment, especially when complexed with humic acid (HA) to form composite contaminants. As an innovative recycled coagulant aid, Enteromorpha polysaccharides (Ep) were associated with polyaluminum chloride (PACl) (denoted as PACl-Ep) to simultaneously remove CuO nanoparticles, Cu²⁺ and HA in this study. The influence of different Al species coagulants (AlCl₃, PACl_b and PACl_c) and water pH on coagulation performance, floc properties and reaction mechanisms was investigated in detail. Results showed that in the three PACl-Ep systems, PACl_b-Ep gave the highest removal efficiencies for turbidity and Cu²⁺, and the best UV₂₅₄ removal effect was reached by using PACl_c-Ep. Higher contents of Al_b and Al_c contributed to great coagulation performance because of their stronger bridging and sweeping effects. For all the Al species coagulants, alkalescent conditions were more conducive to removing Cu and HA compared to acidic conditions. Additionally, smaller and more agminated flocs with great recovery ability were formed by PACl_b-Ep and PACl_c-Ep systems (bridging and enmeshment effects cooperated with the chelated reticular structure formed by the Ep and Al species). Similarly, due to the increased hydrolysis and hydroxide precipitates, flocs formed under the condition of alkalescence were smaller, denser and stronger compared with weakly acidic conditions.     

新生态MnO2强化混凝去除苯酚的影响因素研究

以苯酚为目标物,考察钙离子、单宁酸、高岭土投量、新生态二氧化锰投量、pH等条件对新生态二氧化锰强化氯化铝混凝去除苯酚的影响.结果表明,钙离子能够促进新生态二氧化锰强化混凝对苯酚的去除,在钙离子投加范围内（0～1.0mmol.L-1）,苯酚的去除率能提高10%左右;单宁酸与苯酚共存时,能显著促进苯酚的去除,当单宁酸投加1...